Electrode composite material, method for making the same, and lithium ion battery using the same

ABSTRACT

A cathode composite material includes a cathode active material particle having a surface, and a continuous aluminum phosphate layer coated on the surface of the cathode active material particle. A material of the cathode active material particle is spinel type lithium manganese oxide. The present disclosure also relates to a lithium ion battery and a method for making the cathode composite material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims all benefits accruing under 35 U.S.C. §119 fromChina Patent Application No. 201010242522.4, filed on Aug. 2, 2010, No.201010510350.4, filed on Oct. 15, 2010, No. 201010529980.6, filed onNov. 3, 2010, No. 201010242531.3, filed on Aug. 2, 2010, No.201010507158.X, filed on Oct. 14, 2010, No. 201010509983.3, filed onOct. 15, 2010, No. 201010242541.7, filed on Aug. 2, 2010, in the ChinaIntellectual Property Office, the contents of which are herebyincorporated by reference. This application is related tocommonly-assigned applications entitled, “ELECTRODE COMPOSITE MATERIAL,METHOD FOR MAKING THE SAME, AND LITHIUM ION BATTERY USING THE SAME”,filed **** (Atty. Docket No. US34560); “ELECTRODE COMPOSITE MATERIAL,METHOD FOR MAKING THE SAME, AND LITHIUM ION BATTERY USING THE SAME”,filed **** (Atty. Docket No. US34559), “LITHIUM TITANATE COMPOSITEMATERIAL, METHOD FOR MAKING THE SAME, AND LITHIUM ION BATTERY USING THESAME”, filed **** (Atty. Docket No. US34562), “LITHIUM TITANATE IONBATTERY USING THE SAME”, filed **** (Atty. Docket No. US34561). Thisapplication is a continuation of U.S. patent application Ser. No.13/092135, filed on Apr. 21, 2011, entitled, “ELECTRODE COMPOSITEMATERIAL, METHOD FOR MAKING THE SAME, AND LITHIUM ION BATTERY USING THESAME”.

BACKGROUND

1. Technical Field

The present disclosure relates to electrode active materials used inrechargeable lithium ion batteries and, particularly, to an electrodecomposite material, a method for making the same, and a rechargeablelithium ion battery using the same.

2. Description of Related Art

A common method to improve the properties of cathode active materials oflithium batteries is to treat the surface of the materials. For example,compared to untreated LiFePO₄, the carbon coated LiFePO₄ particles hasimproved conductivity. In another example, research has shown thatcomposite material having AlPO₄ coated LiCoO₂ has a relatively highthermodynamic stability.

The method for forming the composite material includes preparing anamount of dispersed small AlPO₄ particles in water, adding large LiCoO₂particles in the water having the small AlPO₄ particles. The small AlPO₄particles adhere to the surface of the large LiCoO₂ particles. The wateris then evaporated and the LiCoO₂ particles with the AlPO₄ particlesabsorbed thereon are heated at about 700° C. to form the compositematerial.

However, AlPO₄ is insoluble in water. Therefore, in the above method,small AlPO₄ particles may not disperse sufficiently in the water andcould aggregate together. Further, when a large amount of the LiCoO₂particles is added in the water, the LiCoO₂ particles added earlier intime will absorb the majority of the AlPO₄ particles in the water, andthe subsequently added LiCoO₂ particles may not have enough AlPO₄particles to absorb. The uneven absorption occurs most often when addinga relatively large amount of LiCoO₂ particles, which is a problem forindustrialization of this composite material. Furthermore, even thoughit may appear that the LiCoO₂ is coated well, a microscopic view of theAlPO₄ may show that the small particles coated on the surface of theLiCoO₂ large particle do not form a uniform AlPO₄ substance layer.Accordingly, the lithium ion battery using the composite material formedby the above method in the cathode electrode has a low cyclingstability, especially in industry use.

What is needed, therefore, is to provide an electrode composite materialhaving a uniform protective layer coated on the electrode activematerials, a method for making the same, and a lithium ion battery usingthe same.

BRIEF DESCRIPTION OF THE DRAWING

Many aspects of the present disclosure can be better understood withreference to the following drawings. The components in the drawings arenot necessarily to scale, the emphasis instead being placed upon clearlyillustrating the principles of the present embodiments.

FIG. 1 is a view of an embodiment of an electrode composite material ofa lithium ion battery.

FIG. 2 shows a Scanning Electron Microscope (SEM) image of an embodimentof AlPO₄ coated LiCoO2 particles.

FIG. 3 shows a Transmission Electron Microscope (TEM) image of anembodiment of a AlPO₄ coated LiCoO₂ particle surface.

FIG. 4 shows a Scanning Electron Microscope (SEM) image on highmagnification of a comparative example of AlPO₄ coated LiCoO₂ particles.

FIG. 5 shows a Scanning Electron Microscope (SEM) image on lowmagnification of the comparative example of AlPO₄ coated LiCoO₂particles.

FIG. 6 is a graph comparing cycle performance testing results of halfcells using the cathode electrode including AlPO₄ coated LiCoO₂particles in Examples 1-4.

FIG. 7 is a graph comparing cycle performance testing results of halfcells using the cathode electrode including AlPO₄ coatedLiNi_(0.5)Mn_(1.5)O₄ particles in Example 6 and uncoatedLiNi_(0.5)Mn_(1.5)O₄ particles.

FIG. 8 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.2V.

FIG. 9 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.3V.

FIG. 10 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.4V.

FIG. 11 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.5V.

FIG. 12 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.6V.

FIG. 13 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including AlPO₄ coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles in Example 9 charged to 4.7V.

FIG. 14 is a graph showing cycle performance testing results of halfcells using the cathode electrode including AlPO₄ coated LiCoO₂particles in Comparative Example 1 and uncoated LiCoO₂ particles.

FIG. 15 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.2V.

FIG. 16 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.3V.

FIG. 17 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.4V.

FIG. 18 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.5V.

FIG. 19 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.6V.

FIG. 20 is a graph showing a cycle performance testing result of a halfcell using the cathode electrode including uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles charged to 4.7V.

DETAILED DESCRIPTION

The disclosure is illustrated by way of example and not by way oflimitation in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that referencesto “another,” “an,” or “one” embodiment in this disclosure are notnecessarily to the same embodiment, and such references mean at leastone.

Referring to FIG. 1, one embodiment of an electrode composite material10 of a lithium ion battery includes an electrode active materialparticle 12 and an AlPO₄ layer 14 coated on a surface of the electrodeactive material particle 12. A mass percentage of the AlPO₄ layer 14 tothe electrode composite material 10 can be in a range from about 0.1% toabout 3%. A thickness of the AlPO₄ layer 14 can be in a range from about5 nanometers (nm) to about 20 nm. The AlPO₄ layer 14 is an in situformed layer on the surface of the electrode active material particle12, and is a continuous material layer of AlPO₄ having a uniformthickness. Further, the interfacial diffusion may occur at the interfacebetween the AlPO₄ layer 14 and the electrode active material particle12, and transition metal atoms of the electrode active material particle12 may diffuse into the AlPO₄ layer 14.

In one embodiment, the electrode composite material 10 is a cathodecomposite material. The cathode composite material includes a pluralityof cathode composite particles. One cathode composite particle includesa cathode active material particle as the electrode active materialparticle 12 and an AlPO₄ layer 14 coated on a surface of the cathodeactive material particle.

In another embodiment, the electrode composite material 10 is an anodecomposite material. The anode composite material includes a plurality ofanode composite particles. One anode composite particle includes ananode active material particle as the electrode active material particle12 and an AlPO₄ layer 14 coated on a surface of the anode activematerial particle.

The cathode active material particle can be spinel type lithiummanganese oxide, olivine type lithium iron phosphate, layered typelithium manganese oxide, layered type lithium nickel oxide, layered typelithium cobalt oxide, layered type lithium nickel manganese oxide,layered type lithium nickel cobalt manganese oxide, or any combinationthereof. The lithium transition metal oxide can be doped or undoped.

The layered type lithium nickel oxide can be represented by a chemicalformula of Li_(x)Ni_(1-y)L_(y)O₂ (1). The layered type lithium cobaltoxide can be represented by a chemical formula of Li_(x)CO_(1-y)L_(y)O₂(2). The layered type lithium manganese oxide can be represented by achemical formula of Li_(x)Mn_(1-y)L_(y)O₂ (3). The olivine type lithiumiron phosphate can be represented by a chemical formula ofLi_(x)Fe_(1-y)L_(y)PO₄ (4). The layered type lithium nickel manganeseoxide can be represented by a chemical formula ofLi_(x)Ni_(0.5+z-a)Mn_(1.5−z-b)L_(a)R_(b)O₄ (5). The layered type lithiumnickel cobalt manganese oxide can be represented by a chemical formulaof Li_(x)Ni_(c)CO_(d)Mn_(e)L_(f)O₂ (6). The spinel type lithiummanganese oxide can be represented by a chemical formula ofLi_(x)Mn_(2-i)L_(i)O₄ (7). In the aforementioned chemical formulas (1)through (7), 0.1≦x≦1.1, 0≦y<1, 0≦z<1.5, 0≦a−z<0.5, 0≦b+z<1.5, 0<c<1,0<d<1, 0<e<1, 0≦f≦0.2, c+d+e+f=1, and 0≦i<2. M and R represent at leastone of the chemical elements of alkali metal elements, alkaline-earthmetal elements, Group-13 elements, Group-14 elements, transition metalelements, and rare-earth elements. In one embodiment, L and R representat least one of the chemical elements of manganese (Mn), nickel (Ni),chromium (Cr), cobalt (Co), vanadium (V), titanium (Ti), aluminum (Al),iron (Fe), gallium (Ga), neodymium (Nd), and magnesium (Mg). In oneembodiment, 0≦z<0.1. In another embodiment, 0.1<y<0.5.

The anode active material particle can be lithium titanate, graphite,acetylene black, organic cracking carbon, mesocarbon microbeads (MCMB),or any combination thereof. More specifically, the lithium titanate canbe doped or undoped spinel lithium titanate. The undoped lithiumtitanate can be represented by a chemical formula of Li₄Ti₅O₁₂. Thedoped lithium titanate can be represented by a chemical formula ofLi_((4-g))A_(g)Ti₅O₁₂ (8) or Li₄A_(h)Ti_((5-h))O₁₂ (9), wherein 0<g≦0.33and 0<h≦0.5. In the formulas (8) and (9), A represents at least one ofthe chemical elements of alkali metal elements, alkaline-earth metalelements, Group-13 elements, Group-14 elements, transition metalelements, and rare-earth elements. In one embodiment, A represents atleast one of the chemical elements of Mn, Ni, Cr, Co, V, Ti, Al, Fe, Ga,Nd, and Mg.

In one embodiment, the material of the electrode active materialparticle 12 can be layered type lithium cobalt oxide (Li_(x)CoO₂),layered type lithium manganese oxide (Li_(x)MnO₂), or olivine typelithium iron phosphate (Li_(x)FePO₄). In another embodiment, thematerial of the electrode active material particle 12 can be representedby one of chemical formulas of LiNi_(0.5)Mn_(1.5)O₄,LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, and LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂.

A diameter of the electrode active material particle 12 can be in arange from about 100 nanometers to about 100 microns. In one embodiment,the diameter of the electrode active material particle 12 can be in arange from about 1 micron to about 20 microns.

One embodiment of a method for preparing the electrode compositematerial 10 of the lithium ion battery includes steps of:

-   -   S1, providing an aluminum nitrate (Al(NO₃)₃) solution;    -   S2, introducing a plurality of electrode active material        particles 12 into the Al(NO₃)₃ solution, and mixing the        plurality of electrode active material particles 12 with the        Al(NO₃)₃ solution to form a mixture;    -   S3, adding a phosphate solution into the mixture to react with        the Al(NO₃)₃ solution and form an aluminum phosphate layer on        surfaces of the electrode active material particles 12; and    -   S4, heat treating the electrode active material particles 12        with the aluminum phosphate layer formed on the surfaces        thereof.

The Al(NO₃)₃ solution includes liquid phase solvent and Al(NO₃)₃dissolved in the solvent. The solvent can dissolve the Al(NO₃)₃,dissociating the Al(NO₃)₃ into Al³⁺ and NO₃ ⁻. Therefore, the solvent isnot limited to water, and can be other volatile organic solvent. In oneembodiment, the solvent can be at least one of ethanol, acetone,chloroform, diethyl ether, dichloromethane, and ethylidene chloride. Areaction may occur between the electrode active material particles 12and the water thereby deteriorating the performance of the electrodeactive material particles 12. The organic solvent may avoid thisunwanted reaction.

In the step S2, the electrode active material particles 12 cannot bedissolved in the Al(NO₃)₃ solution. A mixing of the electrode activematerial particles 12 and the Al(NO₃)₃ solution forms a mixturecontaining both liquid phase and solid phase. In the mixture, a layer ofAl³⁺ is uniformly coated on the surface of the electrode active materialparticle 12. The Al³⁺ ions can be uniformly adhered to the surface ofthe electrode active material particle 12 to form a coating layer at theatomic level. Further, the amount of the electrode active materialparticles 12 introduced to the Al(NO₃)₃ solution can be controlledaccording to the amount of the Al³⁺ ions in the Al(NO₃)₃ solution, suchthat the amount of the Al³⁺ ions is just sufficient to coat all thesurfaces of the electrode active material particles 12. The mixture canbe pasty. The pasty mixture is formed when the amount of the Al(NO₃)₃solution is just enough to coat the entire surfaces of the electrodeactive material particles 12. The pasty mixture can be formed bycontrolling a volumetric ratio of the Al(NO₃)₃ solution and theelectrode active material particles 12. In one embodiment, thevolumetric ratio of the Al(NO₃)₃ solution and the electrode activematerial particles 12 can be in a range from about 1:10 to about 1:40. Adiameter of the electrode active material particles 12 can be smallerthan 20 microns. The amount of the Al(NO₃)₃ in the mixture can bedetermined from the amount of the aluminum phosphate layer to be formedon the surface of the electrode active material particles 12. In oneembodiment, a mass percentage of the aluminum phosphate layer in theelectrode composite material 10 can be in a range from about 0.1% toabout 3%.

In the step S3, the phosphate solution includes a liquid phase solvent(e.g., water), and a phosphate that can dissolve in the solvent. Thephosphate can be monoammonium phosphate (NH₄H₂PO₄), diammonium phosphate((NH₄)₂HPO₄), ammonium phosphate ((NH₄)₃PO₄), phosphoric acid (H₃PO₄),or combinations thereof. The phosphate solution can include phosphateradical ions such as phosphate ion (PO₄ ³⁻), dihydrogen phosphate ion(H₂PO₄ ⁻), hydrogen phosphate ion (HPO₄ ²⁻), and combinations thereof,dissociated from the phosphate. The phosphate solution is added to thepasty mixture and the phosphate radical ions react with the Al³⁺ locatedabout the surface of the electrode active material particle 12. Thus, auniform aluminum phosphate layer can be formed on the surface of theelectrode active material particle 12 in situ. In one embodiment, thephosphate solution can be added to the pasty mixture drop by drop, whilestirring the mixture, to react the phosphate radical ions entirely andevenly with the Al³⁺ on the surface of the electrode active materialparticle 12. Similar to the AlPO₄ solution, the amount of the phosphatesolution can be determined from the amount of the aluminum phosphatelayer to be formed on the surface of the electrode active materialparticle 12.

In the step S4, the heat treating step can firmly combine the aluminumphosphate layer and the electrode active material particle 12 at theinterfaces therebetween, to form the electrode composite material.Meanwhile, the residual solvent and other reacting products (e.g.ammonium nitrate (NH₄NO₃)) can be removed from the final product. Inaddition, interface diffusion between the aluminum phosphate layer andthe electrode active material particle 12 may be occurred during theheat treating. The transition metal atoms of the electrode activematerial particle 12 may be diffused into the aluminum phosphate layer.The heat treating temperature can be in a range from about 400° C. toabout 800° C. A heat treating time period can be in a range from about0.5 hours to about 2 hours.

In the method, the electrode active material particles 12 are previouslyintroduced to the Al(NO₃)₃ solution, and then the phosphate is added toreact with the Al³⁺ on the surfaces of the electrode active materialparticles 12, to in situ form the AlPO₄ layer coated on the electrodeactive material particles 12. The liquid phase of Al(NO₃)₃ solution ismixed with the solid phase of electrode active material particles 12.Therefore, the Al³⁺ can be uniformly coated on the surfaces of theelectrode active material particles 12. Accordingly, the in situ formedaluminum phosphate layer can also be uniformly coated on the surfaces ofthe electrode active material particles 12. Instead of forming the AlPO₄particles and then absorbing the AlPO₄ particles by the surfaces of theelectrode active material particles 12, the present method avoids theuneven absorption between the solid phase of AlPO₄ and the solid phaseof electrode active material particles 12. Therefore, the present methodavoids an uneven coating of the electrode active material particles 12.By using the method, the AlPO₄ layer 14 can coat a single electrodeactive material particle 12, and each of the electrode active materialparticles 12 that is subsequently introduced can have the AlPO₄ layer 14coated on the surface thereof. Thus, the method is suitable forindustrialization. In addition, the in situ formed AlPO₄ layer 14 is anintegrated and continuous material layer having uniform thickness, notjust a plurality of AlPO₄ particles joined together. In the lithium ionbattery, the AlPO₄ layer 14 can prevent an electron migration betweenthe electrolyte and the electrode active material particles 12 and allowthe lithium ions to pass therethrough. Thus, the side reaction duringthe charge and discharge of the lithium ion battery between theelectrolyte and the electrode active material particles 12 can besuppressed. Therefore, the electrode composite material has improvedchemical and thermal stabilities, even at a relatively high or lowcharge/discharge voltage, or a high rate.

One embodiment of a lithium ion battery includes a cathode, an anode,and a non-aqueous electrolyte disposed between the cathode and theanode. The cathode electrode includes a cathode current collector and acathode material layer disposed on a surface of the cathode currentcollector. The anode electrode includes an anode current collector andan anode material layer disposed on a surface of the anode currentcollector.

In one embodiment, the cathode material layer can include at least oneof the aforementioned cathode composite materials, a conductive agent,and a binder. In another embodiment, the anode material layer caninclude at least one of the aforementioned anode composite materials, aconductive agent, and a binder. The conductive agent can be at least oneof acetylene black, carbon fibers, carbon nanotubes, and graphite. Thebinder can be at least one of polyvinylidene fluoride (PVDF),polytetrafluoroethylene (PTFE), and styrene-butadiene rubber (SBR). Thenon-aqueous electrolyte can be a solid film or a solution including alithium salt dissolved in an organic solvent. The lithium salt may be atleast one of LiPF₆, LiBOB, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃,Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiSbF₆, LiAlO₄, LiAlCl₄, LiCl, and LiI. Theorganic solvent can be a cyclic carbonate and linear carbonate, and canbe at least one of ethylene carbonate (EC), propylene carbonate (PC),ethylmethyl carbonate (EMC), diethyl carbonate (DEC), and dimethylcarbonate (DMC). The lithium ion battery can further include a porousmembrane or a separator located between the cathode electrode and theanode electrode. The material of the separator can be polypropylene (PP)or polyethylene (PE). The lithium ion battery can further include anexterior encapsulating structure such as a hard battery case or a softencapsulating bag. The lithium ion battery can further include aconnecting component achieving an electrical connection between thecurrent collector of the lithium ion battery and the external circuit.

EXAMPLES Cathode Composite Material Example 1

In Example 1, the cathode composite material is an AlPO₄—LiCoO₂composite material including LiCoO₂ particles and an AlPO₄ layer 14coated on a surface of each of the LiCoO₂ particles. The mass percentageof the AlPO₄ layer in the cathode composite material is about 1%.

In the method of preparing the cathode composite material, Al(NO₃)₃ isdissolved in ethanol to form the Al(NO₃)₃ solution. 100 g of LiCoO₂particles is introduced to the 30 mL and 0.16 mol/L of Al(NO₃)₃solution, and stirred to form a pasty mixture. Water solution of(NH₄)₂HPO₄ is added to the pasty mixture drop by drop. Then, the mixtureis uniformly stirred until the AlPO₄ is totally precipitated on thesurfaces of the LiCoO₂ particles. The LiCoO₂ particles coated by theAlPO₄ layer are heated at about 400° C. Referring to FIG. 2 of the SEMphoto, in the product, the AlPO₄ layer is uniformly coated on thesurface of the LiCoO₂ particle. Referring to FIG. 3 of the TEM photo,the AlPO₄ layer formed is a material layer having uniform thicknesscoated on the surface of the LiCoO₂ particle.

Example 2

In Example 2, the cathode composite material is an AlPO₄—LiCoO₂composite material prepared in the same method as in Example 1, exceptfor heating the LiCoO₂ particles coated by the AlPO₄ layer at about 500°C.

Example 3

In Example 3, the cathode composite material is an AlPO₄—LiCoO₂composite material prepared in the same method as in Example 1, exceptfor heating the LiCoO₂ particles coated by the AlPO₄ layer at about 600°C.

Example 4

In Example 4, the cathode composite material is an AlPO₄—LiCoO₂composite material prepared in the same method as in Example 1, exceptthat the mass percentage of the AlPO₄ layer in the cathode compositematerial is about 1.5% and the LiCoO₂ particles coated by the AlPO₄layer are heated at about 600° C.

Example 5

In Example 5, the cathode composite material is an AlPO₄—LiMn₂O₄composite material including LiMn₂O₄ particles and an AlPO₄ layer 14coated on a surface of each of the LiMn₂O₄ particles. The AlPO₄—LiMn₂O₄composite material is prepared in the same method as in Example 3,except that the LiCoO₂ particles in Example 3 are replaced by theLiMn₂O₄ particles.

Example 6

In Example 6, the cathode composite material is anAlPO₄—LiNi_(0.5)Mn_(1.5)O₄ composite material includingLiNi_(0.5)Mn_(1.5)O₄ particles and an AlPO₄ layer 14 coated on a surfaceof each of the LiNi_(0.5)Mn_(1.5)O₄ particles. TheAlPO₄—LiNi_(0.5)Mn_(1.5)O₄ composite material is prepared in the samemethod as in Example 3, except that the LiCoO₂ particles in Example 3are replaced by the LiNi_(0.5)Mn_(1.5)O₄ particles, and the masspercentage of the AlPO₄ layer in the cathode composite material is about0.5%.

Example 7

In Example 7, the cathode composite material is an AlPO₄—LiNiO₂composite material including LiNiO₂ particles and an AlPO₄ layer 14coated on a surface of each of the LiNiO₂ particles. The AlPO₄—LiNiO₂composite material is prepared in the same method as in Example 4,except that the LiCoO₂ particles in Example 4 are replaced by the LiNiO₂particles.

Example 8

In Example 8, the cathode composite material is anAlPO₄—LiNi_(0.8)CO_(0.15)Al_(0.05)O₂ composite material includingLiNi_(0.8)CO_(0.15)Al_(0.05)O₂ particles and an AlPO₄ layer 14 coated ona surface of each of the LiNi_(0.8)CO_(0.15)Al_(0.05)O₂ particles. TheAlPO₄—LiNi_(0.8)CO_(0.15)Al_(0.05)O₂ composite material is prepared inthe same method as in Example 4, except that the LiCoO₂ particles inExample 4 are replaced by the LiNi_(0.8)CO_(0.15)Al_(0.05)O₂ particles.

Example 9

In Example 9, the cathode composite material is anAlPO₄—LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ composite material includingLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles and an AlPO₄ layer 14 coated on asurface of each of the LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles. TheAlPO₄—LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ composite material is prepared in thesame method as in Example 3, except that the LiCoO₂ particles in Example3 are replaced by the LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles.

Anode Composite Material Example 10

In Example 10, the anode composite material is an AlPO₄—Li₄Ti₅O₁₂composite material including Li₄Ti₅O₁₂ particles and an AlPO₄ layer 14coated on a surface of each of the Li₄Ti₅O₁₂ particles. TheAlPO₄—Li₄Ti₅O₁₂ composite material is prepared in the same method as inExample 4, except that the LiCoO₂ particles in Example 4 are replaced bythe Li₄Ti₅O₁₂ particles.

Comparative Example 1

In Comparative Example 1, a comparative cathode composite material isprepared by using a conventional method. In the method, a water solutionof (NH₄)₂HPO₄ and a water solution of Al(NO₃)₃ are mixed together andstirred to form a mixture including a plurality of small AlPO₄ particlesdispersed in water. LiCoO₂ particles are added to the mixture, and theAlPO₄ particles are absorbed to the surfaces of the LiCoO₂ particles.The LiCoO₂ particles having the AlPO₄ particles absorbed thereon arefiltered and heated at about 600° C., to form the comparative cathodecomposite material. Referring to FIG. 4 and FIG. 5, in the product, theAlPO₄ is in a particle shape aggregated on the surface of the LiCoO₂particle. The AlPO₄ particles are aggregated together, and the coatingis not uniform.

Comparative Example 2

In Comparative Example 2, a comparative cathode composite material isprepared in the same method as in Comparative Example 1, except that theLiCoO₂ particles in the Comparative Example 1 are replaced by theLiMn₂O₄ particles.

Comparative Examples 3 and 4

In the Comparative Examples 3 and 4, a comparative cathode compositematerial is prepared in the same method as in Comparative Example 1,except that the LiCoO₂ particles in Comparative Example 1 arerespectively replaced by the LiNiO₂ and LiNi_(0.8)CO_(0.15)Al_(0.05)O₂particles.

Comparative Example 5

In Comparative Example 5, a comparative anode composite material isprepared in the same method as in Comparative Example 1, except that theLiCoO₂ particles in Comparative Example 1 are replaced by the Li₄Ti₅O₁₂particles.

Electrochemical Experiment 1

A half cell is assembled by using the cathode composite material formedin Example 1. The cathode composite material formed in Example 1,acetylene carbon black as a conductive agent, and polyvinylidenefluoride (PVDF) as a binder are mixed in N-methylpyrrolidone (NMP) in amass ratio of about 90:5:5, to form a slurry. The slurry was applied tothe surface of an aluminum foil and dried at about 100° C. to removeNMP, and achieve the cathode electrode. The anode electrode is lithiummetal. 1 mol/L LiPF₆/EC+DEC (1:1) is used as an electrolyte solution.The separator is a porous polypropylene film. The assembled half cell iscycled at a current of about 0.5 C (C-rate) between a discharge cut-offvoltage of 2.7V and a charge cut-off voltage of 4.5V at roomtemperature.

Electrochemical Experiment 2-4

Three half cells are assembled and cycled according to the sameconditions as in the Electrochemical Experiment 1, except that thecathode composite material formed in Example 1 is respectively replacedby the cathode composite materials in Examples 2-4.

Referring to FIG. 6, the half cells of Examples 1-4 all use uniformlycoated LiCoO₂ particles with AlPO₄ layer as the cathode active material,and have relatively high capacity in and capacity retention (i.e.,capacity maintenance rate). After 50 cycles, the capacity retentions ofthe half cells are all above 90%, and the capacities are in a range fromabout 160 mAh/g to about 175 mAh/g. The half cell having the higher heattreating temperature has a higher capacity. However, the change in masspercentage of the AlPO₄ layer in the cathode composite material from 1%to 1.5% did not have much effect to the capacity of the half cell. TheAlPO₄ layer modifies the surface structure of the LiCoO₂, provides alithium intercalation/deintercalation platform, and works as a barrierlayer to suppress the chemical reaction between Co⁴⁺ and theelectrolyte. Thus, the AlPO₄ layer improves the stability of the LiCoO₂,and the cycling performance of the lithium ion battery is improved.

Electrochemical Experiment 5

A half cell is assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the cathode composite material inExample 5. The half cell has a relatively high capacity and capacityretention at both room temperature and a relatively high temperature(e.g., from about 15° C. to about 60° C.). The half cell is cycled at acurrent of about 0.2 C (C-rate) between a discharge cut-off voltage of3V and a charge cut-off voltage of 4.2V at about 55° C. After 50 cycles,the capacity retentions of the half cell are above 90%, and the capacityis about 125 mAh/g.

Electrochemical Experiment 6

A half cell is assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the cathode composite material inExample 6. The half cell is cycled at a current of 0.2 C (C-rate)between a discharge cut-off voltage of 3V and a charge cut-off voltageof 5V at about room temperature. After 50 cycles, the capacityretentions of the half cell are above 95%, and the capacity is about 138mAh/g. Referring to FIG. 7, the half cell is cycled at a current ofabout 1 C (C-rate) between 3V and 5V at about room temperature. After 50cycles, the capacity retentions of the half cell are still above 95%,and the capacity is about 132 mAh/g.

Electrochemical Experiment 7

A half cell is assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the cathode composite material inExample 7. The half cell is cycled at a current of about 0.5 C (C-rate)between a discharge cut-off voltage of 2.5V and a charge cut-off voltageof 4.5V at about room temperature. After 50 cycles, the capacityretentions of the half cell are above 85%, and the capacity is about 150mAh/g.

Electrochemical Experiment 8

A half cell is assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the cathode composite material inExample 8. The half cell is cycled at a current of about 0.5 C (C-rate)between a discharge cut-off voltage of 3.75V and a charge cut-offvoltage of 4.5V at about room temperature. After 50 cycles, the capacityretentions of the half cell are above 91%, and the capacity is about 140mAh/g.

Electrochemical Experiments 9 to 14

Six same half cells are assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the cathode composite material inExample 9. The half cells are cycled 100 times at a current of about 1 C(C-rate) at about room temperature. Experiment results of the charge anddischarge voltage conditions and the capacity retentions are shown inTable 1 and FIGS. 8-13.

TABLE 1 Electrochemical Corre- Charge Discharge Experiment spondingCut-off Cut-off Capacity Number Figure Voltage (V) Voltage (V) Retention9 FIG. 8  4.2 2.7 96.8% 10 FIG. 9  4.3 2.7 81.9% 11 FIG. 10 4.4 2.7 84%12 FIG. 11 4.5 2.7 91.96% 13 FIG. 12 4.6 2.7 90.6% 14 FIG. 13 4.7 2.777.64%

As shown in Table 1, by charging to different voltages, the half cellsall can have a relatively acceptable capacity retention at the currentof 1 C. The capacity retention is about 90.6% when the half cell ischarged to 4.6V which is a relatively high charge voltage.

Electrochemical Experiment 15

A half cell is assembled according to the same conditions as inElectrochemical Experiment 1, except that the cathode composite materialformed in Example 1 is replaced by the anode composite material inExample 10. The half cell has a relatively high capacity and capacityretention at both room temperature and a relatively high temperature(e.g., from about 15° C. to about 60° C.). The half cell is cycled at acurrent of about 0.1 C (C-rate) between a discharge cut-off voltage of0.8V and a charge cut-off voltage of 3V at about 55° C. After 50 cycles,the capacity retentions of the half cell are above 85%, and the capacityis about 160 mAh/g.

Comparative Experiment 1

A Half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 1, except that the cathode compositematerial formed in Example 1 is replaced by uncoated LiCoO₂ particles.

Comparative Experiment 2

A half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 1, except that the cathode compositematerial formed in Example 1 is replaced by the comparative cathodecomposite material in Comparative Example 1.

Referring to FIG. 14, the half cells of the comparative cathodecomposite material in Comparative Example 1 and the uncoated LiCoO₂particles both have a rapid drop of capacity. After 50 cycles, thecapacity retentions of the two half cells are both smaller than 85%.This is mainly because the uneven coating or uncoated LiCoO₂ isrelatively unstable at relative high charge cut-off voltage (e.g.,4.5V). At the high charge cut-off voltage, the LiCoO₂ may have a sidereaction with the electrolyte, to decrease the capacity.

Comparative Experiment 3

A half cell is assembled and cycled according to the same conditions asin the Electrochemical Experiment 5, except that the cathode compositematerial formed in Example 5 is replaced by the comparative cathodecomposite material in Comparative Example 2. The half cell is cycled ata current of about 0.2 C (C-rate) between a discharge cut-off voltage of3V and a charge cut-off voltage of 4.2V at about 55° C. After 50 cycles,the capacity retentions of the half cell are below 85%.

Comparative Experiment 4

A half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 6, except that the cathode compositematerial formed in Example 6 is replaced by the uncoatedLiNi_(0.5)Mn_(1.5)O₄ particles. Referring to FIG. 7, the half cell iscycled at a current of about 1 C (C-rate) between a discharge cut-offvoltage of 3V and a charge cut-off voltage of 5V at room temperature.After 50 cycles, the capacity retentions of the half cell are about 85%,and the capacity is about 118 mAh/g.

Comparative Experiment 5

A half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 7, except that the cathode compositematerial formed in Example 7 is replaced by the comparative cathodecomposite material in Comparative Example 3. After 50 cycles, thecapacity retentions of the half cell are below 85%.

Comparative Experiment 6

A half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 8, except that the cathode compositematerial formed in Example 8 is replaced by the comparative cathodecomposite material in Comparative Example 4. After 50 cycles, thecapacity retentions of the half cell are below 85%.

Comparative Experiments 7 to 12

Six half cells are assembled and cycled according to the same conditionsas in Electrochemical Experiments 9 to 14, except that the cathodecomposite material formed in Example 9 is replaced by the comparativecathode composite material in the uncoated LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂particles. The half cells are cycled 100 times at a current of about 1 C(C-rate) at about room temperature. Experiment results of the charge anddischarge voltage conditions and the capacity retentions are shown inTable 2 and FIGS. 15-20

TABLE 2 Comparative Corre- Charge Discharge Experiment sponding Cut-offCut-off Capacity Number Figure Voltage (V) Voltage (V) Retention 7 FIG.15 4.2 2.7 71.1% 8 FIG. 16 4.3 2.7 70.36% 9 FIG. 17 4.4 2.7 78.14% 10FIG. 18 4.5 2.7 84.87% 11 FIG. 19 4.6 2.7 72.4% 12 FIG. 20 4.7 2.7 54.1%

Referring to FIGS. 15 to 20, when the charge cut-off voltages arerelatively low (e.g., at 4.4V and 4.5V), the cycling curves arerelatively smooth, and after 100 cycles, the capacity retentions areabove 78%. However, when the charge cut-off voltages are increased(e.g., 4.6V and 4.7V), the capacities apparently drop, especially after70 cycles. This may because the LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particlesare uncoated. When the half cell using the uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles is charged to a high voltage, theinternal resistance increases, and the charge and discharge efficiencydecreases, to decrease the capacity of the half cell.

Comparing experiment results of the half cells as shown in FIGS. 8 to 13using the cathode composite material of Example 9 with FIGS. 15 to 20using the uncoated LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles, under thesame conditions, the half cells using the coatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles has smoother cycling curves andhigher capacity retentions than the half cells using the uncoatedLiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ particles.

Comparative Experiment 13

A half cell is assembled and cycled according to the same conditions asin Electrochemical Experiment 15, except that the cathode compositematerial formed in Example 10 is replaced by the comparative cathodecomposite material in Comparative Example 5. After 50 cycles, thecapacity retentions of the half cell are below 85%.

Depending on the embodiment, certain steps of methods described may beremoved, others may be added, and the sequence of steps may be altered.It is also to be understood that the description and the claims drawn toa method may include some indication in reference to certain steps.However, the indication used is only to be viewed for identificationpurposes and not as a suggestion as to an order for the steps.

Finally, it is to be understood that the above-described embodiments areintended to illustrate rather than limit the present disclosure.Variations may be made to the embodiments without departing from thespirit of the present disclosure as claimed. Elements associated withany of the above embodiments are envisioned to be associated with anyother embodiments. The above-described embodiments illustrate the scopeof the present disclosure but do not restrict the scope of the presentdisclosure.

1. A cathode composite material comprising a cathode active materialparticle and a continuous aluminum phosphate layer coated on the surfaceof the cathode active material particle, wherein a material of thecathode active material particle is spinel type lithium manganese oxide.2. The cathode composite material of claim 1, wherein a mass percentageof the continuous aluminum phosphate layer is in a range from about 0.1%to about 3%.
 3. The cathode composite material of claim 1, wherein amass percentage of the continuous aluminum phosphate layer is about 1%.4. The cathode composite material of claim 1, wherein a thickness of thecontinuous aluminum phosphate layer is in a range from about 5nanometers to about 20 nanometers.
 5. The cathode composite material ofclaim 1, wherein the continuous aluminum phosphate layer has a uniformthickness.
 6. The cathode composite material of claim 1, wherein thecontinuous aluminum phosphate layer is an in situ formed layer on thesurface of the cathode active material particle.
 7. The cathodecomposite material of claim 1, wherein a diameter of the cathode activematerial particle is in a range from about 100 nanometers to about 100microns.
 8. The cathode composite material of claim 1, wherein adiameter of the cathode active material particle is in a range fromabout 1 micron to about 20 microns.
 9. The cathode composite material ofclaim 1, wherein the continuous aluminum phosphate layer and the cathodeactive material particle are diffused at an interface between thecontinuous aluminum phosphate layer and the cathode active materialparticle.
 10. The cathode composite material of claim 1, wherein thespinel type lithium manganese oxide is represented by a chemical formulaof Li_(x)Mn_(2-i)L_(i)O₄, wherein 0.1≦x≦1.1 and 0≦i<2, L represents atleast one of the chemical elements of alkali metal elements,alkaline-earth metal elements, Group-13 elements, Group-14 elements,transition metal elements, and rare-earth elements.
 11. The cathodecomposite material of claim 10, wherein L represents at least one of thechemical elements of manganese, nickel, chromium, cobalt, vanadium,titanium, aluminum, iron, gallium, neodymium, and magnesium.
 12. Alithium ion battery comprising: an anode electrode; a cathode electrodecomprising a cathode composite material comprising a plurality ofcathode active material particles and a continuous aluminum phosphatelayer coated on the surface of the plurality of cathode active materialparticles; and a non-aqueous electrolyte disposed between the cathodeand the anode, wherein a material of the cathode active materialparticle is spinel type lithium manganese oxide.
 13. The lithium ionbattery of claim 12, wherein the cathode electrode comprises a cathodecurrent collector and a cathode material layer disposed on a surface ofthe cathode current collector, the cathode material layer comprising thecathode composite material, a conductive agent, and a binder.
 14. Thelithium ion battery of claim 12, wherein a capacity retention is above90% after about 50 cycles at a temperature of about 15° C. to about 60°C.
 15. A method for preparing a cathode composite material, the methodcomprising: providing an aluminum nitrate solution; introducing aplurality of cathode active material particles into the aluminum nitratesolution; mixing the plurality of cathode active material particles withthe aluminum nitrate solution to form a mixture, a material of theplurality of cathode active material particles being spinel type lithiummanganese oxide; adding a phosphate solution into the mixture to reactwith the aluminum nitrate solution and form an aluminum phosphate layeron surfaces of the plurality of cathode active material particles; andheat treating the plurality of cathode active material particles withthe aluminum phosphate layer formed on the surfaces thereof.
 16. Themethod of claim 15, wherein a volumetric ratio of the aluminum nitratesolution and the plurality of cathode active material particles iscontrolled to make the mixture pasty.
 17. The method of claim 16,wherein the volumetric ratio of the aluminum nitrate solution and theplurality of cathode active material particles is in a range from about1:10 to about 1:40.
 18. The method of claim 15, wherein the aluminumnitrate solution comprises a liquid phase solvent and an aluminumnitrate dissolved in the solvent.
 19. The method of claim 15, whereinthe phosphate solution comprises a liquid phase solvent and a phosphatedissolved in the solvent, the phosphate is selected from the groupconsisting of monoammonium phosphate, diammonium phosphate, ammoniumphosphate, phosphoric acid, and combinations thereof.
 20. The method ofclaim 15, wherein the heat treating temperature is in a range from about400° C. to about 800° C.